WO2022210638A1 - 粘着テープ - Google Patents
粘着テープ Download PDFInfo
- Publication number
- WO2022210638A1 WO2022210638A1 PCT/JP2022/015265 JP2022015265W WO2022210638A1 WO 2022210638 A1 WO2022210638 A1 WO 2022210638A1 JP 2022015265 W JP2022015265 W JP 2022015265W WO 2022210638 A1 WO2022210638 A1 WO 2022210638A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- pressure
- sensitive adhesive
- meth
- adhesive layer
- weight
- Prior art date
Links
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 104
- 239000010410 layer Substances 0.000 claims abstract description 78
- 239000000853 adhesive Substances 0.000 claims abstract description 40
- 230000001070 adhesive effect Effects 0.000 claims abstract description 40
- 238000003860 storage Methods 0.000 claims abstract description 32
- 239000002390 adhesive tape Substances 0.000 claims description 34
- 229920000058 polyacrylate Polymers 0.000 claims description 32
- 239000000178 monomer Substances 0.000 claims description 29
- 239000012790 adhesive layer Substances 0.000 claims description 23
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 18
- 239000003431 cross linking reagent Substances 0.000 claims description 15
- 229920001519 homopolymer Polymers 0.000 claims description 10
- 230000009477 glass transition Effects 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical group CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 6
- STFXXRRQKFUYEU-UHFFFAOYSA-N 16-methylheptadecyl prop-2-enoate Chemical compound CC(C)CCCCCCCCCCCCCCCOC(=O)C=C STFXXRRQKFUYEU-UHFFFAOYSA-N 0.000 claims description 4
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 30
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- 239000011347 resin Substances 0.000 description 22
- 229920005989 resin Polymers 0.000 description 22
- 239000000203 mixture Substances 0.000 description 18
- -1 polyethylene terephthalate Polymers 0.000 description 18
- 125000000524 functional group Chemical group 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 238000004132 cross linking Methods 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 3
- 229920005601 base polymer Polymers 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- CUXGDKOCSSIRKK-UHFFFAOYSA-N 7-methyloctyl prop-2-enoate Chemical compound CC(C)CCCCCCOC(=O)C=C CUXGDKOCSSIRKK-UHFFFAOYSA-N 0.000 description 1
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
Definitions
- the present invention relates to adhesive tapes.
- Patent Literature 1 describes a re-peelable pressure-sensitive adhesive tape for packaging having, on at least one surface of a base material, a pressure-sensitive adhesive layer made of a specific pressure-sensitive adhesive containing a plasticizer.
- Such an adhesive tape is desired to be easily peelable without damaging the adherend, but if the adhesive strength is too low, the tape will peel during use.
- the adhesive tape may not adhere sufficiently to the adherend.
- the stickiness to a non-smooth surface can be improved by increasing the thickness of the pressure-sensitive adhesive layer, in general, the thicker the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape, the higher the adhesive strength. For this reason, it has been difficult to obtain a pressure-sensitive adhesive layer that can be sufficiently attached to an adherend and that can be easily peeled off from the adherend while having a certain thickness or more.
- An object of the present invention is to provide a pressure-sensitive adhesive tape which has excellent sticking properties to non-smooth surfaces such as paper and which can be easily peeled off without damaging the adherend.
- the present invention is a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer, wherein the pressure-sensitive adhesive layer has a shear storage elastic modulus of 1 ⁇ 10 4 Pa or more and 5 ⁇ 10 4 Pa or less at 23° C. and 1 Hz, and 180°
- the adhesive tape has an adhesive strength of 0.3 N/25 mm or more and 0.7 N/25 mm or less and a thickness of 30 ⁇ m or more.
- the present inventors have found that in a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer with a thickness of 30 ⁇ m or more, the shear storage modulus of the pressure-sensitive adhesive layer at 23° C. and 1 Hz is adjusted to a specific relatively low range, and the pressure-sensitive adhesive layer Consideration was given to adjusting the 180° tack to a specific, relatively low range.
- the present inventors have found that such an adhesive tape has an adhesive layer having a certain thickness or more, has excellent adhesion to non-smooth surfaces such as paper, and can be easily applied without damaging the adherend.
- the inventors have found that the film can be peeled off easily, and have completed the present invention.
- the adhesive tape of the present invention is an adhesive tape having an adhesive layer.
- the pressure-sensitive adhesive layer has a shear storage modulus at 23° C. and 1 Hz with a lower limit of 1 ⁇ 10 4 Pa and an upper limit of 5 ⁇ 10 4 Pa. If the shear storage elastic modulus is 1 ⁇ 10 4 Pa or more, the shape can be sufficiently retained even if the pressure-sensitive adhesive layer has a certain thickness or more. When the shear storage elastic modulus is 5 ⁇ 10 4 Pa or less, the pressure-sensitive adhesive layer easily conforms to a non-smooth surface such as paper, thereby improving the sticking property.
- the preferred lower limit of the shear storage modulus is 1.5 ⁇ 10 4 Pa
- the preferred upper limit is 4 ⁇ 10 4 Pa
- the more preferred lower limit is 1.7 ⁇ 10 4 Pa
- the more preferred upper limit is 3 ⁇ 10 4 Pa.
- a more preferable lower limit is 2 ⁇ 10 4 Pa.
- the shear storage modulus of the pressure-sensitive adhesive layer at 23° C. and 1 Hz can be measured, for example, using a viscoelastic spectrometer (DVA-200, manufactured by IT Keisoku Kogyo Co., Ltd.), etc., using a simple heating mode with a heating rate of 5° C. It can be obtained as the storage elastic modulus at 23°C when the dynamic viscoelasticity spectrum is measured from -40 to 140°C under the condition of 1 Hz/min.
- the shape of the measurement sample at this time is not particularly limited, for example, the pressure-sensitive adhesive layer can be measured as a rectangular shape with a thickness of 1 mm, a length of 10 mm and a width of 6 mm.
- the pressure-sensitive adhesive layer has a 180° adhesive strength with a lower limit of 0.3 N/25 mm and an upper limit of 0.7 N/25 mm.
- the 180° adhesive strength is 0.3 N/25 mm or more, the adhesive layer has appropriate adhesive strength, and the sticking property to non-smooth surfaces such as paper is improved. If the 180° adhesive strength is 0.7 N/25 mm or less, the adhesive strength of the adhesive layer is sufficiently low, so that it can be easily peeled without damaging the adherend during peeling (re-peeling). .
- a preferred lower limit of the 180° adhesive strength is 0.35 N/25 mm, a preferred upper limit is 0.65 N/25 mm, a more preferred lower limit is 0.4 N/25 mm, and a more preferred upper limit is 0.6 N/25 mm.
- the 180° adhesive strength of the adhesive layer can be measured by the following method. Adhesive tape pre-cut to a width of 25 mm and a length of 10 cm is pasted on a polyethylene terephthalate plate of 50 mm in width, 12.5 cm in length and 2 mm in thickness (for example, product name PET-6010 manufactured by Takiron C.I., or equivalent). A sample for measurement is obtained by combining and reciprocating a 2 kg roller once.
- the obtained measurement sample for example, using an autograph (manufactured by Shimadzu Corporation) or the like, according to JIS Z0237: 2009, polyethylene at a tensile speed of 300 mm / min under an environment of a temperature of 23 ° C. and a relative humidity of 50%.
- a peeling test is performed by peeling the adhesive tape off the terephthalate plate in the direction of 180°, and the 180° adhesive strength (N/25 mm) is measured.
- the shear storage modulus at 23 ° C. and 1 Hz of the pressure-sensitive adhesive layer and the 180 ° adhesive strength to the above ranges, for example, the composition and molecular weight (weight average molecular weight) of the base polymer contained in the pressure-sensitive adhesive layer (Mw)), etc., and a method of adjusting the degree of cross-linking (gel fraction) of the pressure-sensitive adhesive layer.
- the adhesive layer is not particularly limited, and examples thereof include an acrylic adhesive layer, a rubber-based adhesive layer, a urethane-based adhesive layer, a silicone-based adhesive layer, and the like.
- an acrylic pressure-sensitive adhesive layer containing a (meth)acrylic polymer is preferable from the viewpoints of easy adjustment of molecular weight, degree of crosslinking, etc., and excellent heat resistance, weather resistance, cost, and the like.
- the (meth)acrylic polymer is a polymer containing structural units derived from (meth)acrylic monomers.
- the (meth)acrylic monomer is not particularly limited, and examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, and pentyl (meth)acrylate.
- a (meth)acrylic acid ester having an alkyl group having 12 or more carbon atoms and having a glass transition temperature (Tg) of 0° C. or less when made into a homopolymer (hereinafter referred to as “(meth)acrylic acid ester (a)” is also preferred). That is, the (meth)acrylic polymer preferably contains a structural unit derived from the (meth)acrylic acid ester (a). Further, a (meth)acrylic acid ester (hereinafter referred to as "(meth) ) Also referred to as “acrylic acid ester (b)”.) is also preferably used in combination.
- the (meth)acrylic polymer further contains structural units derived from the (meth)acrylic ester (b) in addition to the structural units derived from the (meth)acrylic ester (a). is more preferable.
- the (meth)acrylic polymer contains a structural unit having an alkyl group with a relatively long carbon chain
- the pressure-sensitive adhesive layer has a shear storage modulus at 23°C and 1 Hz and a 180° adhesive strength. is easily adjusted within the above range.
- the pressure-sensitive adhesive layer has improved sticking property to a non-smooth surface such as paper, and can be easily peeled off (re-peeled) without damaging the adherend.
- the glass transition temperature (Tg) of the (meth)acrylic acid ester (a) and the (meth)acrylic acid ester (b) is not particularly limited as long as it is 0° C. or lower. From the viewpoint of adjusting the shear storage modulus of and the 180° adhesive strength to a more preferable range, the preferable lower limit is -80°C and the preferable upper limit is -5°C. A more preferable lower limit of the glass transition temperature (Tg) is -70°C, and a more preferable upper limit is -10°C.
- the glass transition temperature (Tg) of the homopolymer is determined by differential scanning calorimetry (T ⁇ Can be measured using a device such as A Instruments Co., Ltd.). More specifically, it is possible to use the value obtained in the 2nd run when the measurement is performed under the conditions of a temperature increase rate of 10° C./min under a nitrogen atmosphere.
- the (meth)acrylic acid ester (a) is not particularly limited, and among the above-mentioned (meth)acrylic monomers, for example, lauryl acrylate (Tg is ⁇ 23° C. when converted to a homopolymer), lauryl methacrylate (homo Tg when converted to a polymer is -65°C). Further examples include isomyristyl acrylate (Tg of -56°C when converted to a homopolymer), isostearyl acrylate (Tg of -18°C when converted to a homopolymer), and the like.
- lauryl acrylate from the group consisting of lauryl acrylate, lauryl methacrylate and isostearyl acrylate, since the shear storage modulus at 23 ° C. and 1 Hz of the pressure-sensitive adhesive layer and the 180 ° adhesive force are easily adjusted to more preferable ranges. At least one selected is preferred. Furthermore, lauryl acrylate is more preferred.
- the content of the structural unit derived from the (meth)acrylic acid ester (a) in the (meth)acrylic polymer is not particularly limited, but the preferred lower limit is 40% by weight.
- the shear storage modulus at 23° C. and 1 Hz and the 180° adhesive strength of the pressure-sensitive adhesive layer are easily adjusted within the above ranges.
- the pressure-sensitive adhesive layer has improved sticking property to a non-smooth surface such as paper, and can be easily peeled off (re-peeled) without damaging the adherend.
- a more preferable lower limit for the content of the structural unit is 45% by weight.
- the upper limit of the content of the structural unit is not particularly limited, but the upper limit is preferably 90% by weight, and the upper limit is more preferably 80% by weight.
- the (meth)acrylic acid ester (b) is not particularly limited, and among the above-mentioned (meth)acrylic monomers, for example, 2-ethylhexyl acrylate (Tg is ⁇ 70° C. when converted to a homopolymer), octyl acrylate (Tg of -65°C when homopolymerized) and the like. Furthermore, isononyl acrylate (Tg is -58°C when converted to homopolymer), isodecyl acrylate (Tg is -62°C when converted to homopolymer), and the like. Among them, 2-ethylhexyl acrylate is preferable because the shear storage modulus of the pressure-sensitive adhesive layer at 23° C. and 1 Hz can easily be adjusted to a more preferable range.
- the content of the structural unit derived from the (meth)acrylic acid ester (b) in the (meth)acrylic polymer is not particularly limited. From the viewpoint of adjusting the shear storage modulus at 23° C. and 1 Hz and the 180° adhesive strength of the pressure-sensitive adhesive layer to more preferable ranges, the preferable lower limit of the content of the structural unit is 20% by weight, and the preferable upper limit is 60. A more preferable lower limit is 30% by weight, and a more preferable upper limit is 50% by weight.
- the (meth)acrylic polymer preferably further contains a structure derived from a crosslinkable functional group-containing monomer. Since the (meth)acrylic polymer contains a structure derived from the crosslinkable functional group-containing monomer, the cohesive force of the pressure-sensitive adhesive layer can be adjusted by cross-linking of the crosslinkable functional group. It becomes easy to adjust the adhesive strength of the layer to the above range, and it becomes easy to adjust the shear storage elastic modulus at 23° C. and 1 Hz to the above range. As a result, the adhesion of the pressure-sensitive adhesive layer to a non-smooth surface such as paper is further improved, and the adhesive layer can be easily peeled off (re-peeled) without damaging the adherend.
- the crosslinkable functional group may or may not be crosslinked, but is more preferably crosslinked. However, even if the structure remains uncrosslinked, the cohesive force of the pressure-sensitive adhesive layer increases due to the interaction between the functional groups.
- crosslinkable functional group-containing monomers examples include monomers containing carboxyl groups, hydroxyl groups, epoxy groups, double bonds, triple bonds, amino groups, amide groups, nitrile groups, and the like. These crosslinkable functional group-containing monomers may be used alone, or two or more of them may be used in combination. Among them, at least one selected from the group consisting of carboxyl group-containing monomers and hydroxyl group-containing monomers is preferable. Hydroxyl group-containing monomers are more preferable because the shear storage modulus of the pressure-sensitive adhesive layer at 23° C. and 1 Hz can be easily adjusted to the above range by cross-linking with an isocyanate-based cross-linking agent.
- the crosslinkable functional group-containing monomer may further contain an alkyl group, an ether group, a carbonyl group, an ester group, a carbonate group, an amide group, a urethane group, or the like.
- Examples of the carboxyl group-containing monomer include (meth)acrylic acid-based monomers such as (meth)acrylic acid.
- Examples of the hydroxyl group-containing monomer include 4-hydroxybutyl (meth)acrylate and 2-hydroxyethyl (meth)acrylate. Glycidyl (meth)acrylate etc. are mentioned as said epoxy-group-containing monomer.
- Examples of the double bond-containing monomer include allyl (meth)acrylate, hexanediol di(meth)acrylate, and the like.
- Examples of the triple bond-containing monomer include propargyl (meth)acrylate.
- Examples of the amide group-containing monomer include (meth)acrylamide.
- the content of the structure derived from the monomer having the crosslinkable functional group is not particularly limited. From the viewpoint of adjustment, the preferable lower limit of the content of the structural unit is 0.1% by weight, and the preferable upper limit is 30% by weight. A more preferable lower limit of the content of the structural unit is 0.5% by weight, and a more preferable upper limit is 25% by weight.
- the content of the structure derived from the hydroxyl group-containing monomer is not particularly limited, but the shear storage modulus of the pressure-sensitive adhesive layer at 23° C. and 1 Hz is adjusted to a more preferable range.
- the preferable lower limit of the content of the structural unit is 1% by weight, and the preferable upper limit is 20% by weight.
- a more preferable lower limit to the content of the structural unit is 3% by weight, and a more preferable upper limit is 10% by weight.
- a monomer mixture containing the (meth)acrylic monomer, the crosslinkable functional group-containing monomer, etc. is radically reacted in the presence of a polymerization initiator, and copolymerized.
- a polymerization method a conventionally known method is used, and examples thereof include solution polymerization (boiling point polymerization or constant temperature polymerization), emulsion polymerization, suspension polymerization, bulk polymerization, and the like.
- the weight average molecular weight (Mw) of the (meth)acrylic polymer is not particularly limited, but the preferred upper limit is 1,000,000.
- the weight average molecular weight (Mw) is 1,000,000 or less, the shear storage elastic modulus at 23° C. and 1 Hz of the pressure-sensitive adhesive layer is easily adjusted to the above range, and the pressure-sensitive adhesive layer has a non-smooth surface such as paper. The sticking property against is further improved.
- a more preferable upper limit of the weight average molecular weight (Mw) is 950,000, and a further preferable upper limit is 900,000.
- the lower limit of the weight-average molecular weight (Mw) is not particularly limited, the preferred lower limit is 400,000, and the more preferred lower limit is 500,000, from the viewpoint of adhesive strength, shape retention property, etc. of the pressure-sensitive adhesive layer.
- the weight average molecular weight of the (meth)acrylic polymer can be determined, for example, by GPC (Gel Permeation Chromatography) in terms of standard polystyrene. More specifically, for example, using “2690 Separations Module” manufactured by Waters as a measuring instrument, "GPC KF-806L” manufactured by Showa Denko as a column, and ethyl acetate as a solvent, a sample flow rate of 1 mL/min, and a column temperature of 40°C. can be measured under the conditions of
- the pressure-sensitive adhesive layer may contain a tackifying resin.
- the tackifying resin include rosin ester-based resins, hydrogenated rosin-based resins, terpene-based resins, terpene phenol-based resins, coumarone-indene-based resins, alicyclic saturated hydrocarbon-based resins, C5-based petroleum resins, and C9-based resins. petroleum resins, C5-C9 copolymer petroleum resins, and the like. These tackifying resins may be used alone or in combination of two or more.
- the content of the tackifying resin is not particularly limited, it is preferable that the tackifying resin is not contained from the viewpoint of easier peeling without damaging the adherend during peeling (re-peeling).
- the preferred upper limit is 10 parts by weight with respect to 100 parts by weight of the resin (for example, (meth)acrylic polymer) that is the main component of the adhesive layer.
- the content of the tackifier resin is 10 parts by weight or less, the adherend can be easily peeled without damaging the adherend during peeling (re-peeling).
- the pressure-sensitive adhesive layer contains a cross-linking agent to form a cross-linked structure between the main chains of the resin (for example, the (meth)acrylic polymer, the tackifier resin, etc.) constituting the pressure-sensitive adhesive layer.
- the cross-linking agent is not particularly limited, and examples thereof include an isocyanate-based cross-linking agent, an aziridine-based cross-linking agent, an epoxy-based cross-linking agent, and a metal chelate-type cross-linking agent.
- the (meth)acrylic polymer contains a structural unit derived from the hydroxyl group-containing monomer, the shear storage modulus of the pressure-sensitive adhesive layer at 23° C.
- the content of the cross-linking agent is preferably 0.01 to 10 parts by weight, preferably 0.1 to 7 parts by weight, relative to 100 parts by weight of the resin (for example, the (meth)acrylic polymer) that is the main component of the pressure-sensitive adhesive layer. Parts by weight are more preferred.
- the pressure-sensitive adhesive layer may further contain an inorganic filler such as fumed silica. By blending the inorganic filler, the cohesive force of the pressure-sensitive adhesive layer can be increased.
- the pressure-sensitive adhesive layer may further contain known additives such as plasticizers, resins, surfactants, waxes and fine particle fillers. These additives may be used alone, or two or more of them may be used in combination.
- the gel fraction of the pressure-sensitive adhesive layer is not particularly limited, but the preferred lower limit is 85% by weight and the preferred upper limit is 95% by weight.
- the preferred lower limit is 85% by weight or more
- the 180° adhesive strength of the pressure-sensitive adhesive layer is easily adjusted to the above range, and when peeling (re-peeling), the adherend is more easily peeled without damaging the adherend. be able to.
- the gel fraction is 95% by weight or less, the shear storage modulus of the pressure-sensitive adhesive layer at 23° C. and 1 Hz is easily adjusted to the above range, and the pressure-sensitive adhesive layer is attached to a non-smooth surface such as paper. Better adhesion.
- a more preferable lower limit of the gel fraction is 86% by weight, a more preferable upper limit is 94% by weight, a still more preferable lower limit is 87% by weight, and a further preferable upper limit is 93% by weight.
- the gel fraction of the adhesive layer can be measured by the following method. Only 0.1 g of the adhesive layer (adhesive composition) is taken out from the adhesive tape, immersed in 50 mL of ethyl acetate, and shaken with a shaker at 200 rpm and a temperature of 23° C. for 24 hours.
- a metal mesh (#200 mesh) is used to separate the ethyl acetate and the pressure-sensitive adhesive composition that has absorbed and swollen the ethyl acetate.
- the adhesive composition after separation is dried at 110° C. for 1 hour.
- the weight of the pressure-sensitive adhesive composition containing the metal mesh after drying is measured, and the gel fraction of the pressure-sensitive adhesive layer is calculated using the following formula.
- Gel fraction (% by weight) 100 x (W 1 - W 2 )/W 0 (W 0 : initial weight of adhesive composition, W 1 : weight of adhesive composition containing metal mesh after drying, W 2 : initial weight of metal mesh)
- the lower limit of the thickness of the pressure-sensitive adhesive layer is 30 ⁇ m.
- the shear storage modulus at 23° C. and 1 Hz of the pressure-sensitive adhesive layer and the 180° pressure-sensitive adhesive strength are adjusted within the above ranges, so that the pressure-sensitive adhesive tape has a certain thickness or more. While having an agent layer, it has excellent sticking property to non-smooth surfaces such as paper, and can be easily peeled off without damaging the adherend. In addition, when the thickness of the pressure-sensitive adhesive layer is reduced, the followability is deteriorated, so that the sticking property of the pressure-sensitive adhesive layer to the adherend may be deteriorated.
- a preferable lower limit of the thickness of the pressure-sensitive adhesive layer is 40 ⁇ m, and a more preferable lower limit is 50 ⁇ m.
- the upper limit of the thickness of the pressure-sensitive adhesive layer is not particularly limited, the upper limit is preferably 200 ⁇ m, more preferably 150 ⁇ m, from the viewpoint of the adhesive strength, shape retention property, etc. of the pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive tape of the present invention may be a non-support type that does not have a substrate, but it is preferably a support type that has a substrate.
- the adhesive tape of the present invention may be a single-sided adhesive tape having an adhesive layer only on one side of the substrate, or a double-sided adhesive tape having an adhesive layer on both sides of the substrate. Although good, it is preferably a single-sided adhesive tape having an adhesive layer on only one side of the substrate.
- the substrate is not particularly limited, and examples of materials for the substrate include polyethylene terephthalate, polyethylene naphthalate, polyacetal, polyamide, polycarbonate, polyphenylene ether, polybutylene terephthalate, ultra-high molecular weight polyethylene, syndiotactic polystyrene, poly Arylate, polysulfone, polyethersulfone, polyphenylene sulfide, polyetheretherketone, polyimide, polyetherimide, fluororesin, liquid crystal polymer and the like.
- polyethylene terephthalate and polyethylene naphthalate are preferable because of their excellent heat resistance.
- the thickness of the base material is not particularly limited, but a preferable lower limit is 5 ⁇ m and a preferable upper limit is 188 ⁇ m. When the thickness of the base material is within the above range, the pressure-sensitive adhesive tape can have appropriate stiffness and excellent handleability.
- a more preferable lower limit of the thickness of the substrate is 12 ⁇ m, and a more preferable upper limit thereof is 125 ⁇ m.
- the pressure-sensitive adhesive tape of the present invention has a pressure-sensitive adhesive layer having a certain thickness or more by adjusting the shear storage modulus at 23° C. and 1 Hz and the 180° adhesive strength of the pressure-sensitive adhesive layer within the above ranges. While having such properties, it has excellent sticking property to non-smooth surfaces such as paper, and can be easily peeled off without damaging the adherend. As a method for adjusting the shear storage modulus at 23° C.
- the composition of the base polymer contained in the pressure-sensitive adhesive layer a method of adjusting the molecular weight (weight average molecular weight (Mw)) and the like, and a method of adjusting the degree of crosslinking (gel fraction) of the pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive layer contains a (meth)acrylic polymer, and the (meth)acrylic polymer contains 40% by weight or more of structural units derived from the (meth)acrylic acid ester (a) described above, It is particularly preferable that the pressure-sensitive adhesive layer has a weight average molecular weight of 1,000,000 or less, a gel fraction of 85% by weight or more and 95% by weight or less, and a thickness of 30 ⁇ m or more.
- a pressure-sensitive adhesive tape having such a pressure-sensitive adhesive layer is also one aspect of the present invention. In such a pressure-sensitive adhesive tape of the present invention, the pressure-sensitive adhesive layer, the (meth)acrylic polymer, etc. are preferably the same as those described above.
- the shear storage modulus at is adjusted to the above range. That is, the pressure-sensitive adhesive layer preferably has a shear storage modulus of 1 ⁇ 10 4 Pa or more and 5 ⁇ 10 4 Pa or less at 23° C. and 1 Hz.
- the use of the pressure-sensitive adhesive tape of the present invention is not particularly limited.
- the adhesive tape which is excellent in the stickiness with respect to non-smooth surfaces, such as paper, and can be peeled easily, without damaging an adherend can be provided.
- Example 1 Preparation of (meth)acrylic polymer A reactor equipped with a thermometer, a stirrer and a condenser was charged with 52 parts by weight of ethyl acetate, and after the atmosphere was replaced with nitrogen, the reactor was heated to initiate reflux. After 30 minutes from the boiling of ethyl acetate, 0.08 part by weight of azobisisobutyronitrile was added as a polymerization initiator. To this, 47.2 parts by weight of 2-ethylhexyl acrylate, 47.5 parts by weight of lauryl acrylate, 5 parts by weight of 4-hydroxybutyl acrylate and 0.3 parts by weight of acrylic acid were added dropwise evenly and gradually over 1 hour and 30 minutes. reacted.
- a viscoelastic spectrometer manufactured by IT Keisoku & Co., Ltd., DVA-200 was used, and a temperature increase rate of 5 ° C./min in a simple temperature increase mode and a condition of 1 Hz- A dynamic viscoelastic spectrum was measured from 40 to 140°C.
- the storage elastic modulus at 23°C was defined as the shear storage elastic modulus at 23°C and 1 Hz of the pressure-sensitive adhesive layer.
- Examples 2 to 12, Comparative Examples 1 to 11 A pressure-sensitive adhesive tape was obtained in the same manner as in Example 1, except that the composition and weight average molecular weight of the (meth)acrylic polymer, and the amount of the cross-linking agent were changed as shown in Tables 1 and 2.
- the cross-linking agent Coronate HX (manufactured by Tosoh Corporation), which is an isocyanate-based cross-linking agent, and Tetrad C (manufactured by Mitsubishi Gas Chemical Company, Inc.), which is an epoxy-based cross-linking agent, were also used.
- Adhesiveness evaluation on non-smooth surfaces Adhesive tapes were attached to the paper surface of Campus Notebook (manufactured by Kokuyo Co., Ltd.) and Japanese paper (Ryuun pattern, manufactured by Kokuyo Co., Ltd.), and crimped by reciprocating a 2 kg roller once. . When only the adhesive tape part is grabbed and lifted, both the notebook paper and Japanese paper are lifted together with the adhesive tape. A case where neither the paper nor the Japanese paper was lifted and the adhesive tape was peeled off was evaluated as x.
- BA butyl acrylate 2-EHA: 2-ethylhexyl acrylate LA: lauryl acrylate LMA: lauryl methacrylate ISTA: isostearyl acrylate 4-HBA: 4-hydroxybutyl acrylate AAc: acrylic acid
- the adhesive tape which is excellent in the stickiness with respect to non-smooth surfaces, such as paper, and can be peeled easily, without damaging an adherend can be provided.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
粘着剤層を厚くすることで非平滑面への貼りつき性を向上させることも考えられるが、一般に粘着テープにおいては、粘着剤層の厚みが厚くなると粘着力が高くなる。このため、一定以上の厚みを有しながら、被着体に充分に貼りつくことができ、かつ、被着体から容易に剥離できる粘着剤層を得ることは困難であった。また、仮に粘着剤層の厚みを保ったまま粘着力を低くしようとすると、粘着剤層の凝集力を高めることが考えられる。しかし、ベースポリマーの分子量を上げたり、粘着剤層の架橋度を高くしたりすると、紙等の表面の平滑性が低い被着体に対して貼りつき性が悪化することがあった。
以下に本発明を詳述する。
上記せん断貯蔵弾性率が1×104Pa以上であれば、上記粘着剤層が一定以上の厚みを有していても充分に形状を保持することができる。上記せん断貯蔵弾性率が5×104Pa以下であれば、上記粘着剤層が紙等の非平滑面に対しても追従しやすくなり、貼りつき性が向上する。上記せん断貯蔵弾性率の好ましい下限は1.5×104Pa、好ましい上限は4×104Paであり、より好ましい下限は1.7×104Pa、より好ましい上限は3×104Paであり、更に好ましい下限は2×104Paである。
なお、粘着剤層の23℃、1Hzでのせん断貯蔵弾性率は、例えば、粘弾性スペクトロメーター(アイティー計測制御社製、DVA-200)等を用い、単純昇温モードの昇温速度5℃/分、1Hzの条件で-40~140℃の動的粘弾性スペクトルを測定した時の23℃における貯蔵弾性率として得ることができる。このときの測定用サンプルの形状は特に限定されないが、例えば、粘着剤層を厚み1mm、縦10mm、横6mmの長方形の形状として測定することができる。
上記180°粘着力が0.3N/25mm以上であれば、上記粘着剤層が適度な粘着力を有し、紙等の非平滑面に対する貼りつき性が向上する。上記180°粘着力が0.7N/25mm以下であれば、上記粘着剤層の粘着力が充分に低いため、剥離(再剥離)時には被着体を破損することなく容易に剥離することができる。上記180°粘着力の好ましい下限は0.35N/25mm、好ましい上限は0.65N/25mmであり、より好ましい下限は0.4N/25mm、より好ましい上限は0.6N/25mmである。
なお、粘着剤層の180°粘着力は、以下の方法により測定することができる。
予め幅25mm、長さ10cmにカットした粘着テープを、幅50mm、長さ12.5cm、厚さ2mmのポリエチレンテレフタレート板(例えば、タキロンシーアイ社製、品名PET-6010、又はその同等品)に貼り合わせ、2kgローラーを1往復させることで測定用サンプルを得る。得られた測定用サンプルについて、例えば、オートグラフ(島津製作所社製)等を用い、JIS Z0237:2009に準じて、温度23℃、相対湿度50%の環境下で300mm/minの引張速度でポリエチレンテレフタレート板に対し180°方向に粘着テープを引き剥がす剥離試験を行い、180°粘着力(N/25mm)を測定する。
上記(メタ)アクリル系モノマーは特に限定されず、例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、ペンチル(メタ)アクリレート、ヘキシル(メタ)アクリレート、ヘプチル(メタ)アクリレート、オクチル(メタ)アクリレート、イソオクチル(メタ)アクリレート、2-エチルへキシル(メタ)アクリレート、ノニル(メタ)アクリレート、イソノニル(メタ)アクリレート、デシル(メタ)アクリレート、ラウリル(メタ)アクリレート、イソミリスチル(メタ)アクリレート、ステアリル(メタ)アクリレート、イソステアリル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、イソボルニル(メタ)アクリレート等が挙げられる。これらの(メタ)アクリル系モノマーは単独で用いられてもよく、2種以上が併用されてもよい。なお、「(メタ)アクリル」とは、アクリル又はメタクリルを意味し、「(メタ)アクリレート」とは、アクリレート又はメタクリレートを意味する。
また、更に、炭素数8以上、12未満のアルキル基を有し、かつ、ホモポリマーとしたときのガラス転移温度(Tg)が0℃以下である(メタ)アクリル酸エステル(以下、「(メタ)アクリル酸エステル(b)」ともいう。)を併用することも好ましい。即ち、上記(メタ)アクリル系ポリマーは、上記(メタ)アクリル酸エステル(a)に由来する構成単位に加えて、更に、上記(メタ)アクリル酸エステル(b)に由来する構成単位を含有することがより好ましい。
上記(メタ)アクリル系ポリマーがこれらの比較的炭素鎖の長いアルキル基を有する構成単位を含有することで、上記粘着剤層の23℃、1Hzでのせん断貯蔵弾性率、及び、180°粘着力が上記範囲に調整されやすくなる。これにより、上記粘着剤層は、紙等の非平滑面に対する貼りつき性がより向上し、剥離(再剥離)時には被着体を破損することなくより容易に剥離することができる。
なお、ホモポリマーとしたときのガラス転移温度(Tg)は、重量平均分子量(Mw)が5000~100万程度又は重合度が50~1万程度のホモポリマーについて、例えば、示差走査熱量測定(ティー・エイ・インスツルメント社製)等を用いて測定することができる。より詳細には、窒素雰囲気下、昇温速度10℃/分の条件で測定を行った際に2nd runで得られる値を用いることができる。
上記構成単位の含有量の上限は特に限定されないが、好ましい上限は90重量%、より好ましい上限は80重量%である。
上記(メタ)アクリル系ポリマーが上記架橋性官能基含有モノマーに由来する構造を含有することで、架橋性官能基の架橋によって上記粘着剤層の凝集力を調整することができるため、上記粘着剤層の粘着力を上記範囲に調整しやすくなり、また、23℃、1Hzでのせん断貯蔵弾性率を上記範囲に調整しやすくなる。これにより、上記粘着剤層の紙等の非平滑面に対する貼りつき性がより向上し、剥離(再剥離)時には被着体を破損することなくより容易に剥離することができるようになる。上記架橋性官能基は架橋されていても架橋されていなくてもよいが、架橋されていることがより好ましい。ただし、架橋されていない構造のままであったとしても、官能基間の相互作用により上記粘着剤層の凝集力が高まる。
なお、上記架橋性官能基含有モノマーは、更に、アルキル基、エーテル基、カルボニル基、エステル基、カーボネート基、アミド基、ウレタン基等を含んでいてもよい。
また、上記(メタ)アクリル系ポリマー中、上記水酸基含有モノマーに由来する構造の含有量は特に限定されないが、上記粘着剤層の23℃、1Hzでのせん断貯蔵弾性率をより好ましい範囲に調整する観点から、上記構成単位の含有量の好ましい下限は1重量%、好ましい上限は20重量%である。上記構成単位の含有量のより好ましい下限は3重量%、より好ましい上限は10重量%である。
上記重量平均分子量(Mw)の下限は特に限定されないが、上記粘着剤層の粘着力、形状保持性等の観点から、好ましい下限は40万、より好ましい下限は50万である。
なお、(メタ)アクリル系ポリマーの重量平均分子量は、例えば、GPC(Gel Permeation Chromatography:ゲルパーミエーションクロマトグラフィ)法により標準ポリスチレン換算にて求めることができる。より具体的には、例えば、測定機器としてWaters社製「2690 Separations Module」、カラムとして昭和電工社製「GPC KF-806L」、溶媒として酢酸エチルを用い、サンプル流量1mL/min、カラム温度40℃の条件で測定することができる。
上記粘着付与樹脂として、例えば、ロジンエステル系樹脂、水添ロジン系樹脂、テルペン系樹脂、テルペンフェノール系樹脂、クマロンインデン系樹脂、脂環族飽和炭化水素系樹脂、C5系石油樹脂、C9系石油樹脂、C5-C9共重合系石油樹脂等が挙げられる。これらの粘着付与樹脂は単独で用いてもよいし、2種以上を併用してもよい。
上記架橋剤は特に限定されず、例えば、イソシアネート系架橋剤、アジリジン系架橋剤、エポキシ系架橋剤、金属キレート型架橋剤等が挙げられる。なかでも、上記(メタ)アクリル系ポリマーが上記水酸基含有モノマーに由来する構成単位を含有する場合、水酸基との架橋によって上記粘着剤層の23℃、1Hzでのせん断貯蔵弾性率を上記範囲に調整しやすいことから、イソシアネート系架橋剤が好ましい。
上記架橋剤の含有量は、上記粘着剤層の主成分となる樹脂(例えば、上記(メタ)アクリル系ポリマー)100重量部に対して0.01~10重量部が好ましく、0.1~7重量部がより好ましい。
なお、粘着剤層のゲル分率は、以下の方法により測定することができる。
粘着テープから粘着剤層(粘着剤組成物)のみを0.1g取り出し、酢酸エチル50mL中に浸漬し、振とう機で温度23度、200rpmの条件で24時間振とうする。振とう後、金属メッシュ(目開き#200メッシュ)を用いて、酢酸エチルと酢酸エチルを吸収し膨潤した粘着剤組成物を分離する。分離後の粘着剤組成物を110℃の条件下で1時間乾燥させる。乾燥後の金属メッシュを含む粘着剤組成物の重量を測定し、下記式を用いて粘着剤層のゲル分率を算出する。
ゲル分率(重量%)=100×(W1-W2)/W0
(W0:初期粘着剤組成物重量、W1:乾燥後の金属メッシュを含む粘着剤組成物重量、W2:金属メッシュの初期重量)
本発明の粘着テープは、上記粘着剤層の23℃、1Hzでのせん断貯蔵弾性率、及び、180°粘着力が上記範囲に調整されていることで、このように一定以上の厚みを有する粘着剤層を有しながら、紙等の非平滑面に対する貼りつき性に優れ、被着体を破損することなく容易に剥離することができる。なお、上記粘着剤層の厚みが薄くなると、追従性が低下するため、上記粘着剤層の被着体に対する貼りつき性が低下することがある。上記粘着剤層の厚みの好ましい下限は40μm、より好ましい下限は50μmである。
上記粘着剤層の厚みの上限は特に限定されないが、上記粘着剤層の粘着力、形状保持性等の観点から、好ましい上限は200μm、より好ましい上限は150μmである。
上記粘着剤層の23℃、1Hzでのせん断貯蔵弾性率、及び、180°粘着力を上記範囲に調整する方法としては、上述したように、例えば、上記粘着剤層に含まれるベースポリマーの組成、分子量(重量平均分子量(Mw))等を調整する方法、上記粘着剤層の架橋度(ゲル分率)を調整する方法等が挙げられる。なかでも、上記粘着剤層が(メタ)アクリル系ポリマーを含有し、該(メタ)アクリル系ポリマーが上述した(メタ)アクリル酸エステル(a)に由来する構成単位を40重量%以上含有し、重量平均分子量が100万以下であり、上記粘着剤層のゲル分率が85重量%以上、95重量%以下であり、厚みが30μm以上であることが特に好ましい。このような粘着剤層を有する粘着テープもまた、本発明の1つである。このような本発明の粘着テープにおいて、上記粘着剤層、上記(メタ)アクリル系ポリマー等は、上述したものと同様であることが好ましく、なかでも特に、上記粘着剤層は、23℃、1Hzでのせん断貯蔵弾性率が上記範囲に調整されていることが好ましい。即ち、上記粘着剤層は、23℃、1Hzでのせん断貯蔵弾性率が1×104Pa以上、5×104Pa以下であることが好ましい。
(1)(メタ)アクリル系ポリマーの調製
温度計、攪拌機、冷却管を備えた反応器に酢酸エチル52重量部を入れて、窒素置換した後、反応器を加熱して還流を開始した。酢酸エチルが沸騰してから、30分後に重合開始剤としてアゾビスイソブチロニトリル0.08重量部を投入した。ここに2-エチルヘキシルアクリレート47.2重量部、ラウリルアクリレート47.5重量部、4-ヒドロキシブチルアクリレート5重量部及びアクリル酸0.3重量部を1時間30分かけて、均等かつ徐々に滴下し反応させた。滴下終了30分後にアゾビスイソブチロニトリル0.1重量部を添加し、更に5時間重合反応させ、反応器内に酢酸エチルを加えて希釈しながら冷却することにより、(メタ)アクリル系ポリマーの溶液を得た。
得られた(メタ)アクリル系ポリマーについて、測定機器としてWaters社製「2690 Separations Module」、カラムとして昭和電工社製「GPC KF-806L」、溶媒として酢酸エチルを用い、サンプル流量1mL/min、カラム温度40℃の条件で重量平均分子量を測定した。
得られた(メタ)アクリル系ポリマーの溶液に、(メタ)アクリル系ポリマー100重量部に対して、イソシアネート系架橋剤としてコロネートL-45(東ソー社製)を固形分が0.8重量部となるように加えて更に充分に撹拌し、粘着剤溶液を得た。得られた粘着剤溶液を、乾燥皮膜の厚さが30μmになるようにアプリケーターを用いて基材としての厚み100μmのポリエチレンテレフタレート(PET)フィルム上に塗工し、110℃で3分間乾燥させることで粘着テープを得た。
粘着テープから粘着剤層(粘着剤組成物)のみを0.1g取り出し、酢酸エチル50mL中に浸漬し、振とう機で温度23度、200rpmの条件で24時間振とうした。振とう後、金属メッシュ(目開き#200メッシュ)を用いて、酢酸エチルと酢酸エチルを吸収し膨潤した粘着剤組成物を分離した。分離後の粘着剤組成物を110℃の条件下で1時間乾燥させた。乾燥後の金属メッシュを含む粘着剤組成物の重量を測定し、下記式を用いて粘着剤層のゲル分率を算出した。
ゲル分率(重量%)=100×(W1-W2)/W0
(W0:初期粘着剤組成物重量、W1:乾燥後の金属メッシュを含む粘着剤組成物重量、W2:金属メッシュの初期重量)
予め幅25mm、長さ10cmにカットした粘着テープを、幅50mm、長さ12.5cm、厚さ2mmのポリエチレンテレフタレート板(タキロンシーアイ社製、品名PET-6010)に貼り合わせ、2kgローラーを1往復させることで測定用サンプルを得た。得られた測定用サンプルについて、オートグラフ(島津製作所社製)を用い、JIS Z0237:2009に準じて、温度23℃、相対湿度50%の環境下で300mm/minの引張速度でポリエチレンテレフタレート板に対し180°方向に粘着テープを引き剥がす剥離試験を行い、180°粘着力(N/25mm)を測定した。
粘着テープについて、粘弾性スペクトロメーター(アイティー計測制御社製、DVA-200)を用い、単純昇温モードの昇温速度5℃/分、1Hzの条件で-40~140℃の動的粘弾性スペクトルを測定した。23℃における貯蔵弾性率を、粘着剤層の23℃、1Hzでのせん断貯蔵弾性率とした。
(メタ)アクリル系ポリマーの組成及び重量平均分子量、並びに、架橋剤の量を表1~2に示したとおりに変更したこと以外は実施例1と同様にして、粘着テープを得た。架橋剤としては、イソシアネート系架橋剤であるコロネートHX(東ソー社製)、エポキシ系架橋剤であるテトラッドC(三菱ガス化学社製)も用いた。
実施例及び比較例で得られた粘着テープについて下記の評価を行った。結果を表1~2に示した。
キャンパスノート(コクヨ社製)の紙面に粘着テープを貼りつけ、20分間静置した。静置後、高速剥離試験機(テスター産業社製)を用い、50M/minの引張速度で180°方向に粘着テープを引き剥がす剥離試験を行った。ノートの紙面の表面が破れなかった場合を〇、破れた場合を×とした。なお、比較例11では、粘着剤層が凝集破壊し、ノートの紙面に粘着剤残渣が残り、剥離できなかった。
キャンパスノート(コクヨ社製)の紙面及び和紙(コクヨ社製、流雲柄)に粘着テープをそれぞれ貼りつけ、2kgローラーを1往復させることで圧着させた。粘着テープ部分のみを掴んで持ち上げ、粘着テープとともにノートの紙も和紙も持ち上がった場合を◎、粘着テープとともにノートの紙は持ち上がったが、和紙は持ち上がらず粘着テープが剥がれた場合を〇、ノートの紙も和紙も持ち上がらず粘着テープが剥がれた場合を×とした。
2-EHA:2-エチルヘキシルアクリレート
LA:ラウリルアクリレート
LMA:ラウリルメタクリレート
ISTA:イソステアリルアクリレート
4-HBA:4-ヒドロキシブチルアクリレート
AAc:アクリル酸
Claims (9)
- 粘着剤層を有する粘着テープであって、
前記粘着剤層は、23℃、1Hzでのせん断貯蔵弾性率が1×104Pa以上、5×104Pa以下であり、180°粘着力が0.3N/25mm以上、0.7N/25mm以下であり、厚みが30μm以上である
ことを特徴とする粘着テープ。 - 前記粘着剤層は、(メタ)アクリル系ポリマーを含有し、
前記(メタ)アクリル系ポリマーは、炭素数12以上のアルキル基を有し、かつ、ホモポリマーとしたときのガラス転移温度が0℃以下である(メタ)アクリル酸エステルに由来する構成単位を40重量%以上含有し、重量平均分子量が100万以下であり、
前記粘着剤層は、ゲル分率が85重量%以上、95重量%以下である
ことを特徴とする請求項1記載の粘着テープ。 - 前記炭素数12以上のアルキル基を有し、かつ、ホモポリマーとしたときのガラス転移温度が0℃以下である(メタ)アクリル酸エステルは、ラウリルアクリレート、ラウリルメタクリレート及びイソステアリルアクリレートからなる群より選択される少なくとも1種を含有することを特徴とする請求項2記載の粘着テープ。
- 前記炭素数12以上のアルキル基を有し、かつ、ホモポリマーとしたときのガラス転移温度が0℃以下である(メタ)アクリル酸エステルは、ラウリルアクリレートを含有することを特徴とする請求項3記載の粘着テープ。
- 前記(メタ)アクリル系ポリマーは、更に、炭素数8以上、12未満のアルキル基を有し、かつ、ホモポリマーとしたときのガラス転移温度が0℃以下である(メタ)アクリル酸エステルに由来する構成単位を含有することを特徴とする請求項2、3又は4記載の粘着テープ。
- 前記(メタ)アクリル系ポリマーは、水酸基含有モノマーに由来する構成単位を1重量%以上含有することを特徴とする請求項1、2、3、4又は5記載の粘着テープ。
- 前記粘着剤層は、イソシアネート架橋剤を含有することを特徴とする請求項1、2、3、4、5又は6記載の粘着テープ。
- 粘着剤層を有する粘着テープであって、
前記粘着剤層は、(メタ)アクリル系ポリマーを含有し、
前記(メタ)アクリル系ポリマーは、炭素数12以上のアルキル基を有し、かつ、ホモポリマーとしたときのガラス転移温度が0℃以下である(メタ)アクリル酸エステルに由来する構成単位を40重量%以上含有し、重量平均分子量が100万以下であり、
前記粘着剤層は、ゲル分率が85重量%以上、95重量%以下であり、厚みが30μm以上である
ことを特徴とする粘着テープ。 - 前記粘着剤層は、23℃、1Hzでのせん断貯蔵弾性率が1×104Pa以上、5×104Pa以下であることを特徴とする請求項9記載の粘着テープ。
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JP2005314513A (ja) * | 2004-04-28 | 2005-11-10 | Nitto Denko Corp | 粘着剤組成物、およびそれを用いてなる表面保護フィルム |
JP2009057394A (ja) * | 2006-08-30 | 2009-03-19 | Dic Corp | 再剥離用粘着シート |
JP2013122036A (ja) * | 2011-11-10 | 2013-06-20 | Nitto Denko Corp | 粘着シート |
JP2015214677A (ja) * | 2014-04-23 | 2015-12-03 | 日本合成化学工業株式会社 | 粘着剤組成物、粘着剤及び粘着シート |
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JP2009057394A (ja) * | 2006-08-30 | 2009-03-19 | Dic Corp | 再剥離用粘着シート |
JP2013122036A (ja) * | 2011-11-10 | 2013-06-20 | Nitto Denko Corp | 粘着シート |
JP2015214677A (ja) * | 2014-04-23 | 2015-12-03 | 日本合成化学工業株式会社 | 粘着剤組成物、粘着剤及び粘着シート |
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